Extensible, multimodal sensor fusion platform for remote, proximal terrain sensing

ABSTRACT

A sensor assembly includes a housing and multiple sensor array segments. A first sensor array segment includes an antenna. A second sensor array segment has a soil temperature sensor, an electrical conductivity (EC) sensor, a moisture sensor, an ion-sensitive field effect transistor (ISFET) nitrate sensor for detecting nitrates in adjacent soil, an ISFET phosphate sensor for detecting phosphates in adjacent soil, an ISFET potassium sensor for detecting potassium in adjacent soil, and an ISFET pH sensor for detecting pH in adjacent soil, and a reference electrode electrically coupled to the first sensor array segment and to the second sensor array segment. The first sensor array segment and the reference electrode can be disposed on opposite sides of the second sensor array segment.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/578,184, filed Sep. 20, 2019 and titled “Extensible, MultimodalSensor Fusion Platform for Remote, Proximal Terrain Sensing,” whichclaims priority to and the benefit of U.S. Provisional PatentApplication No. 62/734,639, titled “ISFET and CHEMFET Based Sub-SoilSensor Assemblies,” filed Sep. 21, 2018; the disclosures of each of theforegoing applications are expressly incorporated by reference herein intheir entireties.

BACKGROUND

Sensors, such as moisture sensors, are used by farmers and gardeners tomeasure soil properties.

SUMMARY

A sensor assembly includes a housing with one or more sensor arraysegments. One sensor array segment includes wireless communicationhardware, such as an antenna, and optionally, also includes an airtemperature sensor, a humidity sensor, and a light sensor. Anothersensor array segment includes a soil temperature sensor, an electricalconductivity (EC) sensor, a moisture sensor, and a sub-array. Thesub-array includes multiple ion-sensitive field-effect transistor(ISFET) sensors including at least one ISFET sensor for pH measurement.At least one ISFET sensor of the sub-array includes a single-layerruggedized membrane or a multi-layer ruggedized membrane for theselective detection of at least one of: ammonium, calcium, carbonate,chloride, nitrate, phosphate, potassium, sodium, or sulfate, in adjacentsoil. A solid-state reference electrode is either electrically coupledto each ISFET sensor or shared via multiplexing circuit. Optionally, anadditional sensor sub-array contains ion-selective electrodes, alsoelectrically coupled to the reference electrode and shared viamultiplexing circuit. The first sensor array segment and the referenceelectrode can be disposed on opposite sides of the second sensor arraysegment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1C are block diagrams showing sensor assembly configurations,according to some embodiments.

FIGS. 2A-2B are drawings of a sensor assembly (front and side views,respectively), according to an embodiment.

FIG. 3 is a drawing of a sensor assembly including three sensor blocks,according to an embodiment.

FIGS. 4A-4B are drawings of a sensor assembly (front and side views,respectively), according to an embodiment.

FIG. 5 is a drawing of a sensor assembly including three sensor blocks,according to an embodiment.

FIGS. 6A-6D are photographs of a sensor assembly including three sensorblocks, according to an embodiment.

FIGS. 7A-7B are schematic drawings of a sensor die, according to anembodiment.

FIG. 8A is a photograph of a sensor die, according to an embodiment.

FIG. 8B is a photograph of a sensor die mounted on a circuit board andencapsulated, according to an embodiment.

FIG. 9 includes schematic drawings of a large reference electrodeassembly, according to an embodiment.

FIG. 10 includes schematic drawings of a small reference electrode,according to an embodiment.

FIG. 11 is a photograph of a large reference electrode, according to anembodiment.

FIG. 12 is a plot showing stability testing data for a referenceelectrode vs. a silver/silver chloride (Ag/AgCl) reference electrode,according to an embodiment.

FIG. 13 is a photograph of a small reference electrode, according to anembodiment.

FIG. 14 is a plot showing test data for a small reference electrode,according to an embodiment.

FIG. 15 is a photograph of a set of encapsulated four-sensor arrayboards, according to an embodiment.

FIG. 16 is a photograph of a set of encapsulated six-sensor arrayboards, according to an embodiment.

FIG. 17 is an ISFET interface circuit, according to an embodiment.

FIG. 18 is an example implementation of the ISFET interface circuit ofFIG. 17.

FIG. 19 is an ISFET multiplexing circuit, according to an embodiment.

FIG. 20 is a plot showing calibration data for a pH ISFET sensor,according to an embodiment.

FIG. 21 is a plot showing calibration data for a nitrate ISFET sensor,according to an embodiment.

FIG. 22 is a plot showing calibration data for a phosphate ISFET sensor,according to an embodiment.

FIG. 23 is a plot showing calibration data for a potassium ISFET sensor,according to an embodiment.

FIG. 24 is a plot showing the effect of sulfate on the performance ofnitrate sensors, according to an embodiment.

FIG. 25 is a plot showing the effect of carbonate on the performance ofnitrate sensors, according to an embodiment.

FIG. 26 is a plot showing the effect of chloride on the performance ofnitrate sensors, according to an embodiment.

FIG. 27 is a plot showing the effect of sodium on the performance ofpotassium sensors, according to an embodiment.

FIG. 28 is a plot showing the effect of calcium on the performance ofpotassium sensors, according to an embodiment.

FIG. 29 is a plot showing the effect of magnesium on the performance ofpotassium sensors, according to an embodiment.

FIG. 30 is a plot showing the effect of ammonium on the performance ofpotassium sensors, according to an embodiment.

FIG. 31 is a plot showing a dynamic response of a nitrate sensor to anapplied dose of nitrate solution, in accordance with some embodiments.

DETAILED DESCRIPTION

Existing soil sensing architectures typically rely on dedicated sensorsthat are designed to detect individual soil properties, such asmoisture. As such, measuring multiple soil properties can becomecumbersome, due to the need to include multiple discrete sensors, withtheir associated overhead (e.g., cabling, electronics, etc.). Moreover,known sensors are often fabricated from materials that rapidly degradein the presence of soil, and therefore can exhibit a relatively shortlifetime and a lack of predictability and stability in theirperformance.

Embodiments of the present disclosure address the above drawbacks ofexisting soil sensor technologies. For example, sensor assemblies of thepresent disclosure include one or multiple sensor blocks, each sensorblock including sensors (e.g., arranged in rows or arrays) for detectinga wide range of soil conditions and nutrients. Sensors of the presentdisclosure include ruggedized, ion-sensitive membranes and areconfigured to withstand soil environments for substantially longer thanknown sensors. In some embodiments, one or more sensors of a sensorassembly is PVC-free. Alternatively or in addition, in some embodiments,a sensor assembly includes a copper-free reference electrode.

A sensor assembly (also referred to herein as a “stake” or “probe”) ofthe present disclosure can include multiple sensors (i.e., a “suite” ofsensors), including, but not limited to, sensors for temperature,humidity, light, soil moisture, electrical conductivity, pH, and one ormore soil nutrients. The nutrients that can be sensed by sensorembodiments of the present disclosure include, but are not limited to,ammonium (NH₄ ⁺), calcium (Ca²⁺), carbon dioxide/carbonates (CO₂, HCO³⁻,and CO₃ ²⁻, depending on pH), chloride (Cl⁻), nitrate (NO₃ ⁻),phosphates (H₃PO₄, H₂PO₄ ⁻, HPO₄ ²⁻, and PO₄ ³⁻, depending on pH),potassium (K⁺), sodium (Na⁺), and sulfate (SO₄ ²⁻).

A wide range of nutrients can be detected using ion-sensitivefield-effect transistor (ISFET) and/or chemically-sensitive field-effecttransistor (ChemFET) sensors. The ISFETs described herein facilitate anextensible, versatile platform for the detection of a wide variety ofsoil nutrients. An ISFET, in its base configuration, can sense protons(W), thereby enabling pH monitoring. Through the deposition of amembrane on the exposed gate of an ISFET, the ISFET can be transformedinto a ChemFET with chemical sensitivity. The sensor assembly can beconfigured to perform real-time or quasi-real-time transmission of keysoil health metrics to the end user, as part of a precision agriculturesystem. Historically, ISFETs or ChemFETs have not been consideredsuitable for use in soil sensing contexts, for example due to durabilityissues, as discussed above. In the present disclosure, however, severalmethods are presented for improving the durability and stability ofsensors, rendering them suitable for agricultural use. Key improvementsinclude improved membrane materials and solid-state reference electrodesdesigned for long lifetimes in soil.

Sensor Assemblies

In some embodiments, the form factor of a sensor assembly (or“platform”) is that of an elongate “stake” (e.g., suitable for insertioninto the ground), with multiple sensors positioned therein and/orthereon at defined levels, for detecting and reporting nutrient levels(and/or other conditions) at corresponding levels/depths in soil. Themultiple sensors can include (but are not limited to): ammonium ISFETsensor(s), calcium ISFET sensor(s), carbonate ISFET sensor(s), chlorideISFET sensor(s), nitrate ISFET sensor(s), phosphate ISFET or electrodesensor(s), potassium ISFET sensor(s), sodium ISFET sensor(s), sulfateISFET sensor(s) and pH ISFET sensors, electrical conductivity (EC)sensor(s), soil moisture sensor(s), and temperature sensor(s). In someembodiments, the platform can include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, or more ISFET sensors, inclusive ofall ranges and values therebetween. The sensor assembly can include oneor more “sensor blocks,” each sensor block including one or moresensors, each sensor block (or an active/exposed region thereof) beingpositioned at a predetermined location in or on a housing of the sensorassembly (e.g., centered at or beginning at about 6″ (15 cm), about 12″(30 cm), about 18″ (45 cm), and/or about 36″ (90 cm) below the groundlevel). Depending on the implementation, some or all sensors in thesensor assembly are configured to be at least partially in directcontact with the soil once installed. In view of their direct contactwith a soil environment during use, sensors (e.g., including sensormembranes) and sensor assemblies (e.g., including sensor assemblyhousings) of the present disclosure are designed to be durable, andresistant to a wide variety of soil environments.

In some embodiments, the sensor assembly includes a suite of sensors ina sensor probe head (or “probe head”), which includes wirelesscommunications hardware and/or wired communications hardware. Each probehead can also include sensors for one or more of: air temperature,humidity, and light. In some such implementations, one or more carbondioxide (CO₂) gas sensors can be located at specific locations on or inthe sensor assembly, for example at approximately 6″ (15 cm) below asurface of the soil. Alternatively, or in addition, in some suchimplementations, oxygen gas (O₂) sensors can be located at specificlocations on or in the sensor probe, for example at approximately 18″(45 cm) below a surface of the soil. Alternatively or in addition,ammonia (NH₃), nitrous oxide (N₂O), or methane (CH₄) gas sensors can belocated at specific locations throughout the probe. A single, commonsolid-state reference electrode can be located at the tip of the sensorstake, or individual reference electrodes may be located near eachsensor array. The reference electrodes can be shared electrically, forexample via multiplexing circuits.

FIGS. 1A-1C are block diagrams showing sensor assembly configurations,according to some embodiments. As shown in FIG. 1A, a sensor assembly100A includes a housing 101, a first sensor array segment 102 (“probehead”), one or more second sensor array segments 112 (“sensorblock(s)”), and a reference electrode 126. The housing 101 can have anyof a variety of different geometries and/or shapes, including but notlimited to: elongate, disc-shaped, circular, sheet-like, and/orplate-like. The first sensor array segment 102 is disposed within thehousing 101, and includes communications-related equipment 104 (e.g.,antenna, transceiver, wired communication components, processor andassociated memory, etc.), and optionally one or more of an airtemperature sensor 106, a humidity sensor 108, and a light sensor 110.The one or more second sensor array segments 112 are disposed within thehousing 101, and include one or more of: a soil temperature sensor 114,an electrical conductivity (EC) sensor 116, a moisture sensor 118, anion-sensitive field effect transistor (ISFET) nitrate sensor 120, anISFET phosphate sensor 122, an ISFET potassium sensor 124, and an ISFETpH sensor 125. The nitrate sensor 120 is configured to detect, duringuse and substantially in real time, nitrates in an adjacent region ofsoil. The phosphate sensor 122 is configured to detect, during use andsubstantially in real time, phosphates in an adjacent region of soil.The potassium sensor 124 is configured to detect, during use andsubstantially in real time, potassium in an adjacent region of soil. ThepH sensor 125 is configured to detect, during use and substantially inreal time, pH in an adjacent region of soil. The reference electrode 126is electrically coupled to each of the first sensor array segment 102and the second sensor array segment(s) 112. The first sensor arraysegment 102 is disposed on a first (left) side of the second sensorarray segment(s) 112, and the reference electrode 126 is disposed on asecond side of the second sensor array segment(s) 112, the second sideof the second sensor array segment(s) 112 opposite the first side of thesecond sensor array segment(s) 112. In some embodiments, one or more ofthe sensor array segment 102, the one or more second sensor arraysegments 112, or the reference electrode 126 is removably coupled to ordisposed within the sensor assembly 100A, such that it can be replaced.The removable coupling can be accomplished via any suitable means, suchas screw-thread engagement, mechanical attachment (e.g., snaps, clamps,etc.), adhesive attachment, press-fit attachment, etc.

FIG. 1B includes elements similar to those of FIG. 1A, but with thefirst sensor array segment 102 disposed outside (and configured to beattached to) the housing 101. FIG. 1C includes elements similar to thoseof FIG. 1A, but with the reference electrode 126 disposed outside (andconfigured to be attached to) the housing 101.

Sensors of the sensor assemblies (e.g., 100A, 100B, 100C) can becalibrated prior to use, as discussed further below with reference toFIGS. 20-23, and the associated calibration curves can be analyzedand/or stored in firmware or remotely. The firmware can reside in one ormore of: the first sensor array segment (e.g., first sensor arraysegment 102), the one or more second sensor array segments (e.g., one ormore second sensor array segments 112), or “the cloud” (i.e., a cloudcomputing network).

Diagrams depicting an individual sensor block 100 (e.g., similar tosensor blocks 112 of FIGS. 1A-1C) coupled to a large reference electrode126 are shown in FIGS. 2A-2B. As shown in FIGS. 2A-2B, a sensor block100 can include a 4-sensor ISFET array with nitrate, phosphate,potassium, and pH ISFET sensors, along with electrical conductivity(EC), soil moisture, and temperature sensors, at each of a plurality ofpositions in/on each sensor block of the sensor assembly. An example ofa sensor assembly having three sensor blocks (such as the sensor blockshown in FIGS. 2A-2B), each coupled to a single common, large referenceelectrode 126, is shown in FIG. 3.

Diagrams depicting an individual sensor block 100 (e.g., similar tosensor blocks 112 of FIGS. 1A-1C) including a mini reference electrode126 are shown in FIGS. 4A-4B. As shown in FIGS. 4A-4B, a sensor block100 includes a 6-sensor ISFET array with nitrate, ammonium, low-pHphosphate, high-pH phosphate, potassium, and pH ISFET sensors, alongwith EC, soil moisture, and temperature sensors, at each of a pluralityof positions in/on each sensor block of the sensor assembly, where eachposition corresponds to a soil depth during use. Substitutions may bemade, where one nutrient sensor is replaced with another, e.g. a sulfateor calcium ISFET sensor may replace the phosphate ISFET sensor(s). Insome such configurations, small, or “mini,” reference electrodes aredisposed adjacent to (rather than incorporated within) each sensorblock, and connected to an associated set of individual ISFET circuitsof the sensor block. An example of a sensor assembly having three sensorblocks (such as the sensor block shown in FIGS. 4A-4B), each coupled toan associated mini reference electrode 126 (rather than to a commonlarge reference electrode), is shown in FIG. 5.

FIGS. 6A-6D are photographs of a constructed sensor assembly includingthree sensor blocks, according to an embodiment.

Sensor Dies

FIGS. 7A-7B are schematic drawings of an example sensor die, accordingto an embodiment. As shown in FIG. 7A, a sensor die can have arectangular shape with a length of about 2,500 micrometers (μm) and awidth of about 5,000 μm. Bond pads of the conductive traces (connectedto one or more ISFETs of the sensor die) can be about 250 μm by about250 μm square. An active region of the sensor die can have a rectangularshape with a size of about 2,000 μm by about 2,500 μm. Sensor dies canbe fabricated on rigid substrates, such as silicon wafers, or onflexible substrates, such as polyethylene terephthalate (PET). Althoughexample geometries for the sensor die are presented in FIG. 7A,deviations from the sizes and/or proportionalities of the various sensordie features can be made without departing from the scope of the presentdisclosure. In some embodiments, the sensor die can have a length ofabout 500 μm, about 1,000 μm, about 1,500 μm, about 2,000 μm, about2,500 μm, about 3,000 μm, about 3,500 μm, about 4,000 μm, about 4,500μm, or about 5,000 μm, inclusive of all ranges therebetween. In someembodiments, the sensor die can have a width of about 500 μm, about1,000 μm, about 1,500 μm, about 2,000 μm, about 2,500 μm, about 3,000μm, about 3,500 μm, about 4,000 μm, about 4,500 μm, or about 5,000 μm,inclusive of all ranges therebetween. In some embodiments, the sensordie can have a thickness of about 100 μm, about 150 μm, about 200 μm,about 250 μm, about 300 μm, about 350 μm, about 400 μm, about 450 μm,about 500 μm, about 550 μm, about 600 μm, about 650 μm, about 700 μm,about 750 μm, about 800 μm, about 850 μm, about 900 μm, about 950 μm,about 1,000 μm (1 mm), about 1,050 μm, about 1,100 μm, about 1,150 μm,about 1,200 μm, about 1,250 μm, about 1,300 μm, about 1,350 μm, about1,400 μm, about 1,450 μm, about 1,500 μm, about 1,550 μm, about 1,600μm, about 1,650 μm, about 1,700 μm, about 1,750 μm, about 1,800 μm,about 1,850 μm, about 1,900 μm, about 2,000 μm (2 mm), inclusive of allranges therebetween

As described above, nutrient sensing, according to some embodiments, canbe achieved via sensor dies using ISFETs or ChemFETs, which are amenableto fabrication via high-volume CMOS processing. A representativegeometry of an ISFET sensor die is shown in the light microscopephotograph of FIG. 8A. These devices evince common transistor-likestructures, however, the metal gate normally associated with atransistor has been removed and left exposed. In some embodiments, it isthe exposed region (see circled region in FIG. 8A) that is disposedadjacent to soil during use, and is responsible for ion or nutrientsensing (e.g., via one or multiple ion-sensitive membranes). The exposedregion prior to membrane deposition can include one or more materialssuch as such as carbon, graphene, carbon nanotubes, or films includingsilicon nitride (Si₃N₄), aluminum oxide (Al₂O₃), or tantalum oxide(Ta₂O₅). The exposed region can be smaller than or larger than theactive region discussed above with reference to FIG. 7A.

There is a design trade-off between allowing a portion of the sensor tocontact the soil or medium of interest, while also protecting sensitiveelectronics. In some embodiments, the electronics are “encapsulated”using a material such as epoxy or resin. A portion of the active regionof the sensor can be left exposed after the encapsulation process iscompleted. This can be accomplished, for example, by “masking” (orotherwise protecting) the desired region to be exposed, such that noencapsulant material is applied thereto during the encapsulation process(e.g., during an “additive” encapsulation process, in which encapsulantmaterial is added to the surface of the die/PCB). Alternatively, or inaddition, the active region of the sensor die is first coated with theencapsulant material, and then a portion of the active region(corresponding to the desired region to be exposed) is exposed through asubtractive process (e.g., dry etching, wet chemical etching, mechanicalremoval, etc.).

An example of an encapsulated ChemFET sensor die mounted on a printedcircuit board (PCB) is shown in the photograph of FIG. 8B. Additionalexamples of encapsulation can be seen in FIG. 15 with a 4-sensorISFET/ChemFET array and FIG. 16 with a set of boards containing 6-sensorISFET/ChemFET arrays.

Ion-Sensitive Membrane Synthesis and Deposition

Matrix Materials and Processing

In some embodiments, membranes (formed from a “matrix material”) aresynthesized and disposed on an exposed gate of a field-effect transistor(FET) for the detection of analytes. The analytes that can be detectedby a membraned FET include, but are not limited to, ammonium, calcium,carbonate, chloride, nitrate, phosphate, potassium, sodium, and sulfate.A matrix material, as defined herein, can include a fluorosilicone (FS)sealant/adhesive, or other polymeric materials having mechanicalproperties that achieve satisfactory ratings under ASTM standards, suchas ASTM D3359 (Standard Test Methods for Rating Adhesion by Tape Test)and ASTM D6677 (Evaluating Adhesion by Knife). For example, membranescan receive a rating of 5A (no peeling or removal) under ASTM D3359 TestMethod A and a rating of 7 or higher under ASTM D6677.

In some embodiments, various additives may be added to the matrixmaterials to tailor electrical properties, for example, the addition ofcarbon black. Prior to the inclusion of ion-selective ionophores andother ionic additives, the FS matrix material can be dissolved in asuitable solvent, such as tetrahydrofuran (THF) or cyclohexanone.Alternatively, matrix materials can include one or more ionophore-dopedconducting polymers (CPs), such as polyaniline (PANT), polypyrrole(PPy), poly(3,4-ethylenedioxythiophene) (PEDOT), orpoly(3-octylthiophene) (POT), as examples. Alternatively or in addition,a sensor array can include FS, CPs, or a mixture thereof.

In some embodiments, membrane solutions including FS or CPs aredispensed on the exposed gate of the field-effect transistor to yield anion-selective membrane. The dispensing of the matrix material onto theexposed gate can include one or more of: screen printing, inkjetprinting, syringe dispensing, etc. The membrane material(s) may beallowed to cure in air or other ambient environments, or via vacuumprocessing. Photocurable membranes may be cured via UV/visible lightexposure.

Ammonium-Sensing Membranes

In some embodiments, to achieve ion selectivity for ammonium (NH₄ ⁺),the ionophore nonactin, monactin, or a mixture thereof is added to thedissolved matrix material. Optionally, the ionic additive potassiumtetrakis(4-chlorophenyl)borate can also be added. The matrix material,in some embodiments, may be present in amounts ranging from about 30% toabout 90% (w/w), with the balance comprising ionophores, ionicadditives, and plasticizers in varying ratios.

Calcium-Sensing Membranes

In some embodiments, to achieve ion selectivity for calcium (Ca²⁺), theionophore diethylN,N′-[(4R,5R)-4,5-dimethyl-1,8-dioxo-3,6-dioxaoctamethylene]bis(12-methylamino-dodecanoate)(ETH 1001), N,N,N′,N′-tetracyclohexyl-3-oxapentanediamide (ETH 129),calcimycin, N,N-dicyclohexyl-N′,N′-dioctadecyl-3-oxapentanediamide (ETH5234),10,19-bis[(octadecylcarbamoyl)methoxyacetyl]-1,4,7,13,16-pentaoxa-10,19-diazacycloheneicosane,α-furildioxime, or a mixture thereof is added to the dissolved matrixmaterial. Optionally, the ionic additive sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB) can also beadded. The matrix material, in some embodiments, may be present inamounts ranging from 30%-90% (w/w) or thereabouts, with the balancecomprising ionophores, ionic additives, and plasticizers in varyingratios.

Carbonate-Sensing Membranes

In some embodiments, to achieve ion selectivity for carbonate (CO₃ ²⁻),the ionophore heptyl 4-trifluoroacetylbenzoate (ETH 6010), 1-(dodecylsulfonyl)-4-trifluoroacetylbenzene (ETH 6019),N-dodecyl-N-(4-trifluoroacetylphenyl)acetamide (ETH 6022),4-butyl-α,α,α-trifluoroacetophenone,N,N-dioctyl-3α,12α-bis(4-trifluoroacetylbenzoyloxy)-5β-cholan-24-amide,or a mixture thereof is added to the dissolved matrix material.Optionally, the ionic additive tridodecylmethylammonium chloride (TDMAC)can also be added. The matrix material, in some embodiments, may bepresent in amounts ranging from 30%-90% (w/w) or thereabouts, with thebalance comprising ionophores, ionic additives, and plasticizers invarying ratios.

Chloride-Sensing Membranes

In some embodiments, to achieve ion selectivity for chloride (Cl⁻), theionophore meso-tetraphenylporphyrin manganese(III)-chloride complex,4,5-dimethyl-3,6-dioctyloxy-o-phenylene-bis(mercurytrifluoroacetate)(ETH 9009), 3,6-didodecyloxy-4,5-dimthyl-o-phenylene-bis(mercurychloride) (ETH 9033),4,5-bis-[N′-(butyl)thioureido]-2,7-di-tert-butyl-9,9-dimethylxanthene,or a mixture thereof is added to the dissolved matrix material.Optionally, the ionic additive tridodecylmethylammonium chloride (TDMAC)can also be added. The matrix material, in some embodiments, may bepresent in amounts ranging from 30%-90% (w/w) or thereabouts, with thebalance comprising ionophores, ionic additives, and plasticizers invarying ratios.

Nitrate-Sensing Membranes

In some embodiments, to achieve ion selectivity for nitrate (NO₃ ⁻), theionophore α,α,α,α-5,10,15,20-tetrakis{2-[3-(4-methylphenyl)ureido]phenyl}porphyrine,1,6,10,15-tetraoxa-2,5,11,14-tetraazacyclooctodecane,[1,3,8,10]tetraazacyclotetradecine-10,21-dithione,9-hexadecyl-1,7,11,17-tetraoxa-2,6,12,16-tetraazacycloeicosane, or amixture thereof is added to the dissolved matrix material. Optionally,tridodecylmethylammonium nitrate, tetradodecylammonium nitrate,tri-n-octylmethylammonium nitrate, or other quaternary ammonium saltsmay can also be added. The matrix material, in some embodiments, may bepresent in amounts ranging from 30%-90% (w/w) or thereabouts, with thebalance comprising ionophores, ionic additives, and plasticizers invarying ratios.

Phosphate-Sensing Membranes

In some embodiments, to achieve ion selectivity for the phosphates inthe pH regime of approximately 2-7, tin organometallics, such astributyltin chloride (TBTC), are added to the dissolved matrix material.Ionic additives such as sodium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate (NaTFPB) may be added in varyingmol % relative to the tin organometallics. To achieve ion selectivityfor the phosphates in the pH regime of approximately 7-12, cyclicpolyamines such as the N₃-, N₄-, N₅-, and N₆-cyclic amines are used asionophores. NaTFPB may be added in varying mol % relative to the cyclicamines. The matrix material, in some embodiments, may be present inamounts ranging from 30%-90% (w/w) or thereabouts, with the balancecomprising ionophores, ionic additives, and plasticizers in varyingratios. In some embodiments, multiple ISFET-based phosphate sensors arecoupled to cover a wider pH range, and these sensors may also becorrelated to electrode-based sensors, such as those fabricated fromcobalt wires, enabling the sensor to detect a broad spectrum ofphosphate species in soil.

Potassium-Sensing Membranes

In some embodiments, to achieve ion selectivity for potassium, theionophore valinomycin is added to the dissolved matrix material.Optionally, the ionic additives potassium tetrakis(4-chlorophenyl)borate(KT4ClPB) and/or sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate(NaTFPB) can also be added. The matrix material, in some embodiments,may be present in amounts ranging from 30%-90% (w/w) or thereabouts,with the balance comprising ionophores, ionic additives, andplasticizers in varying ratios.

Sodium-Sensing Membranes

In some embodiments, to achieve ion selectivity for sodium (Na⁺), theionophoreN,N′,N″-triheptyl-N,N′,N″-trimethyl-4,4′,4″-propylidynetris(3-oxabutyramide)(ETH 227), N,N′-dibenzyl-N,N′-diphenyl-1,2-phenylenedioxydiacetamide(ETH 157), N,N,N′,N′-tetracyclohexyl-1,2-phenylenedioxydiacetamide (ETH2120), 2,3:11,12-didecalino-16-crown-5, bis[(12-crown-4)methyl]dodecylmethylmalonate, bis[(12-crown-4)methyl] 2,2-didodecylmalonate,4-tert-butylcalix[4]arene-tetraacetic acid tetraethyl ester, or amixture thereof is added to the dissolved matrix material. Optionally,the ionic additive sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate(NaTFPB) can also be added. The matrix material, in some embodiments,may be present in amounts ranging from 30%-90% (w/w) or thereabouts,with the balance comprising ionophores, ionic additives, andplasticizers in varying ratios.

Sulfate-Sensing Membranes

In some embodiments, to achieve ion selectivity for sulfate (SO₄ ²⁻),the ionophore 1,3-[bis(3-phenylthioureidomethyl)]benzene,4-(4-bromophenyl)-2,6-diphenylpyrilium perchlorate (BDPP), or a mixturethereof is added to the dissolved matrix material. The matrix material,in some embodiments, may be present in amounts ranging from 30%-90%(w/w) or thereabouts, with the balance comprising ionophores, ionicadditives, and plasticizers in varying ratios.

Reference Electrodes

In some embodiments, where metal gates are removed from the transistorstructures to yield ISFETs/ChemFETs, one or more reference electrodesare added to the sensor assembly, the reference electrode(s) beingconfigured for placement in (and durability within) the same medium asthe ISFETs/ChemFETs (e.g., soil). Traditional reference electrodedesigns often contain liquids that are prone to drying out, and aretypically constructed using glass, further reducing their ruggedness. Bycontrast, reference electrodes of the present disclosure, usingsolid-state electrolytes, address these weaknesses. For example, in someembodiments, the reference electrode assembly contains a “frit” toenable ionic transport from the soil to the solid-state electrolyte; thefrit materials may be comprised of porous ceramic, glass, or polymericmaterials.

Large Reference Electrodes

As shown in FIG. 9, a large reference electrode assembly 126,compatible, for example, with the sensor assemblies of FIGS. 2A-2B andFIG. 3, includes a main body portion with a male connector 132 extendingtherefrom, the male connector 132 configured to connect with (i.e., bereceived by) a female connector 130. FIG. 11 is a photograph of anassembled large reference electrode 126, compatible, for example, withthe sensor assemblies of FIGS. 2A-2B, FIG. 3, or FIGS. 6A-6D, accordingto an embodiment. Assembled reference electrodes of varying electrolytecomposition have been tested against reference Ag/AgCl elements tomonitor their stability of the reference potential and to examinepotential drift. FIG. 12 is a plot showing comparison data for largereference electrodes (“RE's”) vs. a silver/silver chloride (Ag/AgCl)reference electrode, according to an embodiment. As demonstrated by theplot data in FIG. 12, each of the tested reference electrodes (RE1through RE7 and versions of RE1 through RE3 “conditioned” in anelectrolyte storage solution) compared favorably with bare Ag/AgClreference electrodes. The assembly process for large referenceelectrodes is provided in the Example Reference Electrode AssemblyProcess section below.

Small Reference Electrodes

Additional form factors have been developed, including small/miniature(“mini”) versions of the solid-state reference electrode. These aretypically intended to be located near the sensor arrays, rather than atthe tip of the sensor stake. Schematic drawings of a small referenceelectrode 126, compatible, for example, with the sensor assemblies ofFIGS. 4A-4B and FIG. 5. As shown in FIG. 10, a small (or “mini”)reference electrode 126 includes a silver (Ag) electrode 134 positionedwithin a recess formed by sleeve 136 and at least partially supported byan internal cap 138 (which, in some embodiments, is integrally formedwith the sleeve 136). A lid 140 is positioned at the top of the recessformed by sleeve 136. A sensor module PCB 142 (e.g., includingconductive traces and/or electronics) is mechanically attached to thesleeve 136 (or other components of the reference electrode 126) and iselectrically connected to the Ag electrode 134. A photograph of a fullyassembled mini reference electrode is provided in FIG. 13. An example ofwhere the mini reference electrode of FIG. 13 may be located relative tothe overall sensor assembly can be seen, for example, in FIGS. 4A-4B(reference electrode 126—in each instance of a sensor block, multiple ofwhich may be included in an overall sensor assembly) and in FIG. 5(reference electrodes 126—in each instance of a sensor block 100). FIG.14 is a plot showing stability testing data for a small referenceelectrode, according to an embodiment. As demonstrated by the plot datain FIG. 12, there is a “settling” or “equilibration” period (over thefirst ˜0.3 days) during which the potential being measured by thereference electrode decreases (e.g., asymptotically) until it approachesa steady-state value (in this case, about −0.003 V). This“equilibration” period may be taken into account when processing sensorsignals of the sensor assembly, for example by excluding or disregardingdata collected during the “equilibration” period, or making adjustmentsthereto (e.g., based on a time at which the particular data point wasmeasured/detected).

Example Reference Electrode Assembly Process

In some embodiments, a reference electrode includes a housing, a ceramicfrit, a Ag/AgCl element, and a solid electrolyte comprising “Plaster ofParis” (CaSO₄.0.5H₂O) and NaCl. To assemble the reference electrode, theceramic frit (e.g., made of a metal oxide such as alumina (Al₂O₃)) isaffixed to the reference electrode housing, for example using an epoxy(in which case the assembly, one epoxied, is allowed to cure overnight).The Ag/AgCl element is secured to the reference electrode cap using asmall quantity of epoxy to the upper face (where the bare Ag wireoriginates) of the Ag/AgCl element. The bare Ag wire protrudes from thecap and is affixed to a copper (or similar metal) wire using a solder orcrimped connection. The result of this assembly step is the Ag/AgClelement, which is epoxied to the reference electrode cap, which in turnis connected to copper or a similarly conductive wire.

After the ceramic frit is secured to the reference electrode body, asolid electrolyte mixture of deionized water, “Plaster of Paris”(CaSO₄.0.5H₂O), and NaCl is poured into the main cavity in the referenceelectrode housing. Within about one minute, the Ag/AgCl element from thecap-Ag/AgCl assembly is submerged into the solid electrolyte mixtureprior to solidification. The solidification process of the solidelectrolyte material is completed within about approximately twentyminutes. The solid electrolyte composition can be varied based on thetargeted soil under analysis.

Upon installation of the Ag/AgCl element into the solid electrolyte, thecap is epoxied or otherwise secured to the main reference electrodebody, thereby completing the assembly of the reference electrode.

Sensor Arrays

FIG. 15 is a photograph of five encapsulated four-sensor arrays (i.e.,four sensors arranged in a single row per array, with five arrays on asingle board), according to an embodiment. FIG. 16 is a photograph of aset of three encapsulated six-sensor array boards, according to anembodiment.

ISFET Interface Circuit

In some embodiments, the ISFET device operates under a constant-voltage,constant-current bias scheme. A voltage source enforces a constantsource-drain voltage V_(ds) (V_(d)-V_(s)), for example approximately 0.3V. A feedback loop senses the source-drain current through the ISFET(Ids) and adjusts the gate voltage V_(g), until the Ids reaches aspecified current, in some embodiments approximately 25 uA. Thegate-source voltage V_(gs) (V_(g)-V_(s)) is then measured and representsthe output of the sensor. An ISFET interface circuit schematic diagramand example implementation are shown in FIG. 17 and FIG. 18,respectively. In FIG. 17 a voltage source (V_(supply)) defines the ISFETV_(ds) potential. An ammeter senses the current flowing through thevoltage source and the ISFET. Based on the output of the ammeter, acurrent controlled voltage source adjusts the gate voltage, V_(g), toreach the desired ISFET current. In FIGS. 18, U2 and U3 provide stablepositive and negative reference voltages for biasing the ISFET. Theresistors R5, R6, and R7 act as a voltage divider to generate thenecessary V_(ds). The operational amplifier U4A buffers the V_(d)voltage and provides a low output impedance to drive the ISFET. Theresistor R14 is the current sensing element, and together withoperational amplifier U4D, creates the current controlled voltage sourcethat drives the reference electrode (RE) potential. In stable sensingoperation, V_(s) will be approximately 0 V and the output of the sensorcan be read as V_(g).

ISFET Multiplexing

Several ISFET devices may be multiplexed into a single interface circuitthrough standard multiplexing techniques. Here, several lowon-resistance (Ron) single-pole-single-throw solid state switches areused to switch rows connected to drains of ISFET devices and columnsconnected to sources of ISFET devices. Optionally, the referenceelectrode may also be selectively connected to the interface circuitthrough similar switches. These switches may be discrete devices orintegrated into a single package. An example ISFET multiplexing circuitis shown in FIG. 19.

Sensor Calibration (Field and Lab Studies)

Calibration data for pH ISFETs and nitrate, phosphate, and potassiumChemFETs can be seen in FIGS. 20-23, respectively. Testing has beenconducted to assess the selectivity of the ChemFETs toward interferingions. In the case of nitrate sensors, they have been tested againstanions such as sulfates (FIG. 24), carbonates (FIG. 25), and chlorideions (FIG. 26). The potassium sensors have been tested against commoncations found in soil, such as sodium (FIG. 27), calcium (FIG. 28),magnesium (FIG. 29), and ammonium (FIG. 30). Both sensors havedemonstrated strong selectivity toward the ion of interest (e.g.nitrate, potassium) and reject interfering ions. Tests have beenperformed to test the dynamic response of sensors to doses of solutionscontaining the ion of interest in soil. An example of this studyconducted in sand is shown in FIG. 31. Data collected from field studieswith the sensor stakes has been compared to lab-tested samples. Mostresults are within 10 ppm of the lab-derived results.

FIG. 20 is a plot showing calibration data for a pH ISFET sensor,according to an embodiment. During calibration, three measurements ofthe sensor response (in millivolts, mV) were taken, in solution, atthree different associated pH levels (in this case, pH values of about4, about 7, and about 10). The sensor response data was plotted, and aline of best fit was drawn (in this case, y=48.5x+953.8), and acoefficient of determination (R²) was calculated (in this case,R²=0.99858).

FIG. 21 is a plot showing calibration data for a nitrate ISFET sensor,according to an embodiment. During calibration, three measurements ofthe sensor response (in mV) were taken, in solution, at three differentvalues of log([NO₃ ⁻]) (in this case, log([NO₃ ⁻]) values of about −3.0,about −2.0, and about −1.0). The sensor response data was plotted, and aline of best fit was drawn (in this case, y=−50.5x−1100), and acoefficient of determination (R²) was calculated (in this case,R²=0.99971).

FIG. 22 is a plot showing calibration data for a phosphate ISFET sensor,according to an embodiment. During calibration, three measurements ofthe sensor response (in mV) were taken, in solution, at three differentvalues of log([H₂PO₄ ⁻]) (in this case, log([H₂PO₄ ⁻]) values of about−3.0, about −2.0, and about −1.0). The sensor response data was plotted,and a line of best fit was drawn (in this case, y=−49.5x−812.7), and acoefficient of determination (R²) was calculated (in this case,R²=0.99834).

FIG. 23 is a plot showing calibration data for a potassium ISFET sensor,according to an embodiment. During calibration, three measurements ofthe sensor response (in mV) were taken, in solution, at three differentvalues of log([K⁺]) (in this case, log([K⁺]) values of about −3.0, about−2.0, and about −1.0). The sensor response data was plotted, and a lineof best fit was drawn (in this case, y=51.5x−1140), and a coefficient ofdetermination (R²) was calculated (in this case, R²=0.99997).

Sensitivity of Sensors to Contaminants

FIG. 24 is a plot showing the effect of sulfate, as a potentialcontaminant, on the performance of nitrate sensors (using a Ag/AgClreference electrode), according to an embodiment. As shown in FIG. 24,side-by-side comparisons of sequential sensor readings (using fourdistinct sensors, Sensors 1 through 4) for nitrate (NO₃ ⁻) alone (leftportion of each grouping) and nitrate in the presence of sulfate (rightportion of each grouping) are shown for three different ratios ofnitrate to sulfate (i.e., Grouping 1=1 mM nitrate, 10 mM sulfate;Grouping 2=10 mM nitrate, 10 mM sulfate; Grouping 3=100 mM nitrate, 10mM sulfate). The data in FIG. 24 shows that the nitrate sensorperformance was stable even in the presence of sulfate.

FIG. 25 is a plot showing the effect of carbonate, as a potentialcontaminant, on the performance of nitrate sensors (using a Ag/AgClreference electrode), according to an embodiment. As shown in FIG. 25,sequential sensor readings (using four distinct sensors, Sensors 1through 4) for nitrate in the presence of carbonate (CO₃ ²⁻) are shownfor three different ratios of nitrate to CO₃ ²⁻ (i.e., Grouping 1=1 mMnitrate, 10 mM carbonate; Grouping 2=10 mM nitrate, 10 mM carbonate;Grouping 3=100 mM nitrate, 10 mM carbonate). The data in FIG. 25 showsthat the nitrate sensor performance was stable (e.g., Grouping 1,showing negligible/near-zero variation in voltage) or substantiallystable (e.g., Groupings 2 and 3, showing variation in voltage of about0.02-0.04 V), even in the presence of carbonate.

FIG. 26 is a plot showing the effect of chloride, as a potentialcontaminant, on the performance of nitrate sensors (using a Ag/AgClreference electrode), according to an embodiment. As shown in FIG. 26,sequential sensor readings (using four distinct sensors, Sensors 1through 4) for nitrate in the presence of chloride are shown for threedifferent ratios of nitrate to chloride (i.e., Grouping 1=1 mM nitrate,20 mM chloride; Grouping 2=10 mM nitrate, 20 mM chloride; Grouping 3=100mM nitrate, 20 mM chloride). The data in FIG. 26 shows that the nitratesensor performance was stable (e.g., Groupings 2 and 3, showingnegligible/near-zero variation in voltage) or substantially stable(e.g., Grouping 1, showing variation in voltage of about 0.02 V), evenin the presence of chloride.

FIG. 27 is a plot showing the effect of sodium ions (Na^(t)), as apotential contaminant, on the performance of potassium sensors,according to an embodiment. As shown in FIG. 27, sequential sensorreadings (using four distinct sensors, Sensors 1 through 4) forpotassium in the presence of sodium are shown for six different ratiosof potassium to sodium (i.e., Grouping 1=1 mM potassium, 0 mM sodium;Grouping 2=1 mM potassium, 10 mM sodium; Grouping 3=10 mM potassium, 0mM sodium; Grouping 4=10 mM potassium, 10 mM sodium; Grouping 5=100 mMpotassium, 0 mM sodium; Grouping 6=100 mM potassium, 10 mM sodium). Thedata in FIG. 27 shows that the potassium sensor performance was stableor substantially stable, even in the presence of sodium.

FIG. 28 is a plot showing the effect of calcium ions (Ca²⁺), as apotential contaminant, on the performance of potassium sensors,according to an embodiment. As shown in FIG. 28, sequential sensorreadings (using four distinct sensors, Sensors 1 through 4) forpotassium in the presence of calcium are shown for six different ratiosof potassium to calcium (i.e., Grouping 1=1 mM potassium, 0 mM calcium;Grouping 2=1 mM potassium, 10 mM calcium; Grouping 3=10 mM potassium, 0mM calcium; Grouping 4=10 mM potassium, 10 mM calcium; Grouping 5=100 mMpotassium, 0 mM calcium; Grouping 6=100 mM potassium, 10 mM calcium).The data in FIG. 27 shows that the potassium sensor performance wasstable or substantially stable, even in the presence of calcium.

FIG. 29 is a plot showing the effect of magnesium ions (Mg²⁺), as apotential contaminant, on the performance of potassium sensors,according to an embodiment. As shown in FIG. 29, sequential sensorreadings (using four distinct sensors, Sensors 1 through 4) forpotassium in the presence of magnesium are shown for six differentratios of potassium to magnesium (i.e., Grouping 1=1 mM potassium, 0 mMmagnesium; Grouping 2=1 mM potassium, 10 mM magnesium; Grouping 3=10 mMpotassium, 0 mM magnesium; Grouping 4=10 mM potassium, 10 mM magnesium;Grouping 5=100 mM potassium, 0 mM magnesium; Grouping 6=100 mMpotassium, 10 mM magnesium). The data in FIG. 29 shows that thepotassium sensor performance was stable or substantially stable, even inthe presence of magnesium.

FIG. 30 is a plot showing the effect of ammonium (NH₄ ⁺), as a potentialcontaminant, on the performance of potassium sensors, according to anembodiment. As shown in FIG. 30, sequential sensor readings (using fourdistinct sensors, Sensors 1 through 4) for potassium in the presence ofammonium are shown for six different ratios of potassium to magnesium(i.e., Grouping 1=1 mM potassium, 0 mM ammonium; Grouping 2=1 mMpotassium, 10 mM ammonium; Grouping 3=10 mM potassium, 0 mM ammonium;Grouping 4=10 mM potassium, 10 mM ammonium; Grouping 5=100 mM potassium,0 mM ammonium; Grouping 6=100 mM potassium, 10 mM ammonium). The data inFIG. 30 shows that the potassium sensor performance was stable orsubstantially stable, even in the presence of ammonium.

FIG. 31 is a plot showing a dynamic response of a nitrate sensor to anapplied dose of nitrate solution, in accordance with some embodiments.As can be seen in FIG. 31, there is an initial time period (<1,000seconds) during which the sensor is initially “wetted” with thenitrate-containing solution and detects a rapidly increasing amount ofnitrate. After this initial equilibration period, the sensor reaches andmaintains a steady-state detected level of nitrate.

In some embodiments, one or more components of the sensor assembly(e.g., a first sensor array segment or a second sensor array segment)includes a processor and a memory storing instructions to cause theprocessor to one or more of: receive signals from one or more sensors ofthe sensor assembly, analyze signals from one or more sensors of thesensor assembly to detect or calculate a soil parameter, or send signalsto one or more remote computing devices, in response to a sensordetection event. Instructions to analyze signals from one or moresensors of the sensor assembly can include calculating a soil parameterbased at least in part on calibration data associated with the one ormore sensors, and/or based at least in part on a known equilibrationperiod associated with the one or more sensors.

Sensors, sensor assemblies and/or sensor blocks of the presentdisclosure can be configured to interface with (e.g., send data toand/or receive data from) one or more automated irrigation systems,drone inspection systems, and/or other agricultural technology systems,for example to cause a modification to a setting (e.g., relating totemperature, irrigation, etc.) or to trigger an alarm (e.g., forpresentation to a user via a graphical user interface of a mobile ordesktop computing device).

In some embodiments, an apparatus includes a housing and multiple sensorarray segments. The multiple sensor array segments include a firstsensor array segment and a second sensor array segment. The first sensorarray segment can include an antenna, an air temperature sensor, ahumidity sensor, and a light sensor. The second sensor array segment caninclude a soil temperature sensor, an EC sensor, a moisture sensor, anISFET-based pH sensor, and an array of ISFET-based sensors featuringruggedized, single-layer or multi-layer membranes for the selectivedetection of one or a combination of the following soil nutrients:ammonium, calcium, carbonate, chloride, nitrate, phosphate, potassium,sodium, and sulfate, during use and substantially in real time, in anadjacent region of soil. One or both of the first sensor array segmentand the second sensor array segment can be disposed within the housing.The apparatus also includes a reference electrode electrically coupledto each of the first sensor array segment and the second sensor arraysegment. The first sensor array segment can be disposed on a first sideof the second sensor array segment, and the reference electrode can bedisposed on a second side of the second sensor array segment, the secondside of the second sensor array segment opposite the first side of thesecond sensor array segment.

In some embodiments, the apparatus further includes a third sensor arraysegment. The third sensor array segment can include a soil temperaturesensor, an EC sensor, a moisture sensor, an ISFET-based pH sensor, andan array of ISFET-based sensors featuring ruggedized, single- ormulti-layer membranes for the selective detection of one or acombination of the following soil nutrients: ammonium, calcium,carbonate, chloride, nitrate, phosphate, potassium, sodium, and sulfate,during use and substantially in real time, in an adjacent region ofsoil. The second sensor array segment and the third sensor array segmentcan be arranged sequentially, in any order, within the housing.

In some embodiments, the apparatus further includes a third sensor arraysegment and a fourth sensor array segment. One or both of the thirdsensor array and the fourth sensor array can include a soil temperaturesensor, an EC sensor, a moisture sensor, an ISFET-based pH sensor, andan array of ISFET-based sensors featuring ruggedized, single-layer ormulti-layer membranes for the selective detection of one or acombination of the following soil nutrients: ammonium, calcium,carbonate, chloride, nitrate, phosphate, potassium, sodium, and sulfate,during use and substantially in real time, in an adjacent region ofsoil. The second sensor array segment, the third sensor array segment,and the fourth sensor array segment can be arranged sequentially, in anyorder, within the housing.

In some embodiments, the apparatus is configured such that, in use, thedetection of pH by the ISFET pH sensor, the detection of nitrate by theISFET nitrate sensor, and the detection of other soil nutrients, such asammonium, calcium, carbonate, chloride, phosphate, potassium, sodium,and sulfate, are performed sequentially.

In some embodiments, an apparatus includes a housing and an ISFET pHsensor disposed within the housing and configured to detect, during useand substantially in real time, pH in an adjacent region of soil. Theapparatus also includes an ISFET nitrate sensor, disposed within thehousing, configured to detect, during use and substantially in realtime, nitrates in an adjacent region of soil. The apparatus alsoincludes at least one of: an ISFET ammonium sensor disposed within thehousing and configured to detect, during use and substantially in realtime, ammonium in an adjacent region of soil; an ISFET calcium sensordisposed within the housing and configured to detect, during use andsubstantially in real time, calcium in an adjacent region of soil; anISFET carbonate sensor disposed within the housing and configured todetect, during use and substantially in real time, carbonates in anadjacent region of soil; an ISFET chloride sensor disposed within thehousing and configured to detect, during use and substantially in realtime, chloride in an adjacent region of soil; an ISFET phosphate sensordisposed within the housing and configured to detect, during use andsubstantially in real time, an ISFET carbonate sensor disposed withinthe housing and configured to detect, during use and substantially inreal time, carbonate in an adjacent region of soil; an ISFET potassiumsensor disposed within the housing and configured to detect, during useand substantially in real time, potassium in an adjacent region of soil;an ISFET sodium sensor disposed within the housing and configured todetect, during use and substantially in real time, sodium in an adjacentregion of soil; an ISFET sulfate sensor disposed within the housing andconfigured to detect, during use and substantially in real time,sulfates in an adjacent region of soil; or an ISFET phosphate sensordisposed within the housing and configured to detect, during use andsubstantially in real time, phosphates in an adjacent region of soil,and a reference electrode electrically coupled to each of the ISFET pHsensor, the ISFET nitrate sensor, and the at least one of the ISFETpotassium sensor, the ISFET ammonium sensor, or the ISFET phosphatesensor. At least one of the ISFET nitrate sensor, the ISFET pH sensor,and the ISFET potassium sensor can include a fluoropolysiloxanemembrane. The apparatus can be configured such that, in use, thedetection of nitrate by the ISFET nitrate sensor, the detection of pH bythe ISFET pH sensor, and at least one of the detection of potassium bythe ISFET potassium sensor, the detection of ammonium by the ISFETammonium sensor, or the detection of phosphate by the ISFET phosphatesensor, are performed sequentially.

In some embodiments, an apparatus includes a housing, a first sensorarray segment, a second sensor array segment, and a reference electrode.The first sensor array segment can include an antenna, an airtemperature sensor, a humidity sensor, and a light sensor. The secondsensor array segment is disposed within the housing, and includes a soilmoisture sensor, an EC sensor, and an ISFET pH sensor configured todetect, during use and substantially in real time, a pH in an adjacentregion of soil. The reference electrode is electrically coupled to eachof the first sensor array segment and the second sensor array segment.The first sensor array segment is disposed on a first side of the secondsensor array segment, and the reference electrode is disposed on asecond side of the second sensor array segment, the second side of thesecond sensor array segment opposite the first side of the second sensorarray segment. In some implementations, the apparatus also includes athird sensor array segment. The third sensor array segment can include asoil moisture sensor, an EC sensor, and an ISFET nitrate sensor (e.g.,including a fluoropolysiloxane membrane) configured to detect, duringuse and substantially in real time, nitrates in an adjacent region ofsoil. Alternatively, or in addition, the third sensor array segment caninclude a soil moisture sensor, an EC sensor, and an ISFET ammoniumsensor (e.g., including a fluoropolysiloxane membrane) configured todetect, during use and substantially in real time, ammonium in anadjacent region of soil. Alternatively, or in addition, the third sensorarray segment can include a soil moisture sensor, an EC sensor, and anISFET phosphate sensor (e.g., including a fluoropolysiloxane membrane)configured to detect, during use and substantially in real time,phosphates in an adjacent region of soil. Alternatively, or in addition,the third sensor array segment can include a soil moisture sensor, an ECsensor, and an ISFET potassium sensor (e.g., including afluoropolysiloxane membrane) configured to detect, during use andsubstantially in real time, potassium in an adjacent region of soil.

In some embodiments, an apparatus includes a housing, a first sensorarray segment, a second sensor array segment, and a single/common(“shared”) reference electrode. The first sensor array segment includesan antenna, an air temperature sensor, a humidity sensor, and a lightsensor. The second sensor array segment includes a soil moisture sensor,an EC sensor, and an SFET nitrate sensor (e.g., including afluoropolysiloxane membrane) configured to detect, during use andsubstantially in real time, a nitrate in an adjacent region of soil. Thereference electrode is electrically coupled to each of the first sensorarray segment and the second sensor array segment. One or more of thefirst sensor array segment, the second sensor array segment, or thereference electrode is at least partially disposed within the housing.The first sensor array segment can be disposed on a first side of thesecond sensor array segment, and the reference electrode can be disposedon a second side of the second sensor array segment, the second side ofthe second sensor array segment opposite the first side of the secondsensor array segment.

In some embodiments, an apparatus includes a housing, a first sensorarray segment, a second sensor array segment, and a reference electrode.The first sensor array segment includes an antenna, an air temperaturesensor, a humidity sensor, and a light sensor. The second sensor arraysegment is disposed within the housing, and includes a soil moisturesensor, an EC sensor, and an ISFET ammonium sensor configured to detect,during use and substantially in real time, ammonium in an adjacentregion of soil. The reference electrode is electrically coupled to eachof the first sensor array segment and the second sensor array segment.The first sensor array segment is disposed on a first side of the secondsensor array segment, and the reference electrode is disposed on asecond side of the second sensor array segment, opposite the first sideof the second sensor array segment.

In some embodiments, an apparatus includes a housing, a first sensorarray segment, a second sensor array segment, and a reference electrode.The first sensor array segment includes an antenna, an air temperaturesensor, a humidity sensor, and a light sensor. The second sensor arraysegment disposed within the housing, the second sensor array segmentincluding a soil moisture sensor, an EC sensor, and an ISFET phosphatesensor configured to detect, during use and substantially in real time,phosphates in an adjacent region of soil. The reference electrode iselectrically coupled to each of the first sensor array segment and thesecond sensor array segment. The first sensor array segment is disposedon a first side of the second sensor array segment, and the referenceelectrode is disposed on a second side of the second sensor arraysegment, opposite the first side of the second sensor array segment.

In some embodiments, the ISFET phosphate sensor can include a first,ISFET low-pH phosphate sensor, the second sensor array segment furtherincluding a second, ISFET high-pH phosphate sensor.

In some embodiments, an apparatus includes a housing, a first sensorarray segment, a second sensor array segment, and a reference electrode.The first sensor array segment includes an antenna, an air temperaturesensor, a humidity sensor, and a light sensor. The second sensor arraysegment can be disposed within the housing, the second sensor arraysegment including a soil moisture sensor, an EC sensor, and a ISFETpotassium sensor (e.g., including a fluoropolysiloxane membrane)configured to detect, during use and substantially in real time,potassium in an adjacent region of soil. The reference electrode can beelectrically coupled to each of the first sensor array segment and thesecond sensor array segment. The first sensor array segment can bedisposed on a first side of the second sensor array segment, and thereference electrode is disposed on a second side of the second sensorarray segment, opposite the first side of the second sensor arraysegment.

As used herein, the terms “about” and “approximately” generally meanplus or minus 10% of the value stated, for example about 250 μm wouldinclude 225 μm to 275 μm, about 1,000 μm would include 900 μm to 1,100μm.

While various embodiments of the system, methods and devices have beendescribed above, it should be understood that they have been presentedby way of example only, and not limitation. Where methods and stepsdescribed above indicate certain events occurring in a certain order,those of ordinary skill in the art having the benefit of this disclosurewould recognize that the ordering of certain steps may be modified andsuch modification are in accordance with the variations of theinvention. Additionally, certain of the steps may be performedconcurrently in a parallel process when possible, as well as performedsequentially as described above. The embodiments have been particularlyshown and described, but it will be understood that various changes inform and details may be made.

1. An apparatus, comprising: a housing; a first sensor array segment,including an antenna; a second sensor array segment disposed within thehousing, the second sensor array segment including a soil moisturesensor, an EC sensor, and an ISFET nutrient sensor configured to detect,during use and substantially in real time, a nutrient in an adjacentregion of soil; and a reference electrode electrically coupled to eachof the first sensor array segment and the second sensor array segment,the first sensor array segment disposed on a first side of the secondsensor array segment, and the reference electrode disposed on a secondside of the second sensor array segment, the second side of the secondsensor array segment opposite the first side of the second sensor arraysegment.